The present study sets out to elucidate the characteristic features of instantaneous heat transfer accompanying transient superheating of partially miscible mixtures having a lower critical solution temperature (LCST) with respect to the liquid–liquid binodal and the diffusion (liquid–liquid) spinodal. The research has employed the method of controlled pulsed heating of a wire probe, which can be used to directly measure heat flux into the medium at a strictly fixed heater temperature Tst. At a characteristic heating time of 100 ms, values of Tst were gradually increased from 100 to 500 °C, while the corresponding pressures varied from 0.1 to 35 MPa. The objects of study were aqueous solutions of PPG-425 and PPG-2000 polypropylene glycols, as well as 2,6-Lutidine, all having LCST in the range convenient for achieving large superheats. The values of the heat transfer coefficient (whose highest values reached 90 kW/m2 K for the solution with 5 wt% PPG-2000 content at the superheat degree of about 390 °C) and the energy absorbed by the solution were calculated on the basis of the primary data. The calculation results related the individual features of the studied systems to the phase diagram and characteristic system relaxation times depending on the concentration and superheat degree with respect to the spinodal. The applicability of such systems as coolants under conditions of high-power heat release for elements with a short response time is demonstrated. Based on the experimental results, we validated the selection of solutions as coolants in the concentration range from the left branch of the spinodal to the critical concentration of the solution.